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61.
C. Auguet J. L. Seguin F. Martorell F. Moll V. Torra J. Lerchner 《Journal of Thermal Analysis and Calorimetry》2006,86(2):521-529
Micro-calorimetric
devices using Si-based sensors are very useful for the study of gas–solid
reactions, in which very low mass of reactants are necessary. But in fact
the consequence of using flat detectors is an increase of the uncertainty
in the measured energy. In this work a calorimetric gas sensor based on Xensor
chip is analysed studying the local x–y
contributions of dissipation to the sensitivity related to the value in the
centre. We study also the effects of the gas-flow on the sensitivity, comparing
the results obtained with two Xensor type chips. Finally we carry out a deeper
analysis of the x–y effects on the
calorimetric detector for dissipations in the reactant shell extremely close
to the detector surface to visualize the link between the power density distribution
and the output signal. 相似文献
62.
Anna M. Maj Albert Demonceau Alfred F. Noels 《Journal of organometallic chemistry》2007,692(14):3048-3056
A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl2(p-cymene)]2 dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl2(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization. 相似文献
63.
The densities of H2O, D2O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10–6 g cm–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V–
2
) and the isotope effects in V–
2
and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H2O, D2O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility. 相似文献
64.
The absorption spectra of isoquinoline-iodine or 2,4-lutidine-iodine solutions in organic solventsn-hexane,n-heptane, cyclohexane, carbon tetrachloride, benzene, toluene, chlorobenzene, ando-dichlorobenzene have been measured and interpreted in terms of the D+I2=DI2 equilibrium, where D is isoquinoline or 2,4-lutidine. Values ofK (288–320°K), ΔHo, and ΔSo for the reaction were calculated. A correlation between theK values and the solubility parameter of the solvent (Buchowski's relation) has been found. 相似文献
65.
Synthesis and characterization of segmented liquid crystal poly(azoxy polyester-co-polyoxypropylene)
Jaine-Ming Huang Jen-Feng Kuo Chuh-Yung Chen 《Journal of polymer science. Part A, Polymer chemistry》1995,33(1):165-173
In this study a series of a segmented copolyester, poly(4,4′-dioxy-2,2′-dimethyl-azoxybenzene dodecanedioyl) (PMABD)-co-polyoxypropylene 400 (POP), was prepared. The chain length of PMABD studied (n) was varied from 7.8-18.2, and that of POP was unchanged. The intrinsic viscosity of the segmented copolyesters was 1.04-1.30, and the number average molecular weight obtained was 2.53 × 104?3.49 × 104 g/mol. The mesophase texture and thermal properties of the segmented copolyesters were measured as functions of n. It was found that the insert of flexible POP between those liquid crystalline domains of PMABD did affect thermotropic properties of PMABD. As the n value was 9.0 and 7.8 (or 7.4 and 8.6% by weight POP) the texture appeared as cholesteric-like oily streaks. The effect could not be attained by simply copolymerizing a mesogenic moiety with a pair of spacers of different lengths. The fluidity and domain structure of the flexible dodecanedioyl-POP-dodcanedioyl segments are taken into account for the obtained results. © 1995 John Wiley & Sons, Inc. 相似文献
66.
A simple electrostatic analysis is given of the virtual charge (solvaton) model to represent the environment effect on the electronic wave function of a solute immersed in a polarizable surrounding. New features of this model are found. The classical aspects are discussed and secondly the quantal implications are considered. A correct Hartree-Fock-like operator is derived which represents an electron in a molecular orbital subjected to the average effect of the other electrons and to the reaction field produced by the virtual charges on the atomic centers.A general formalism based on the preceding model is presented in appendix. The final equations have a form similar to Newton's equation to represent a solvated electron. Unlike some other theories in this field, there is no cut-off involved in the evaluation of the molecular integrals. 相似文献
67.
68.
Roesky HW Murugavel R Walawalkar MG 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(2):324-331
Metal hydroxides represent a very interesting and highly useful class of compounds that have been known to chemists for a very long time. While alkali and alkaline earth metal hydroxides (s‐block) are commonplace chemicals in terms of their abundance and their use in a chemical laboratory as bases, the interest in Brønsted acidic molecular terminal hydroxides of p‐block elements, such as aluminum and silicon, has been of recent origin, with respect to the variety of applications these compounds can offer both in materials science and catalysis. Moreover, these systems are environmentally friendly, relative to the metal halides, owing to their ‐OH functionality (resembling that of water). Design and conceptualization of the corresponding terminal thiols, selenols, and tellurols (M? SH, M? SeH, and M? TeH) offer even more challenging problems to synthetic inorganic chemists. This concept summarizes some of the recent strategies developed to stabilize these otherwise very unstable species. The successful preparation of a number of silicon trihydroxides a few years back resulted in the generation of several model compounds for metal–silicates. The recent synthesis of unusual aluminum compounds such as RAl(OH)2, RAl(SH)2, and RAl(SeH)2 with terminal EH (E=O, Se, or Se) groups is likely to change the ways in which some of the well‐known catalytic conversions are being carried out. The need for very flexible and innovative synthetic strategies to achieve these unusual compounds is emphasized in this concept. 相似文献
69.
J. Choma H. Jankowska J. Piotrowska M. Jaroniec 《Monatshefte für Chemie / Chemical Monthly》1987,118(3):315-321
A simple isotherm equation for describing gas adsorption on solids showing heterogeneity of microporous structure is proposed. It is shown that this equation gives a good representation of the experimental data of argon, nitrogen and benzene adsorption on different types of activated carbons. Its parameters may be used to characterize heterogeneity of microporous structure of the solids.
Eine einfache Isotherme zur Beschreibung der Gas-Adsorption an heterogenen mikroporösen Feststoffen
Zusammenfassung Es wird eine einfache Isotherme zur Beschreibung der Gasadsorption an Feststoffen mit heterogener mikroporöser Struktur vorgeschlagen. Es wird gezeigt, daß diese Gleichung die experimentellen Daten für die Adsorption von Argon, Stickstoff und Benzol an verschiedenen Typen von Aktivkohle gut beschreibt. Die Parameter der Isotherme können zur Charakterisierung der Heterogenität der mikroporösen Struktur von Festkörpern herangezogen werden.相似文献
70.
M. P. Carril M. Soledad Corbillón J. Manuel Madariaga 《Accreditation and quality assurance》1997,2(6):301-308
The development of an analytical method for the determination of some heavy metals (Fe, Cu, Co, Zn and Ni) in fluoride compounds
[Cu(BF4)2, Sn(BF4)2, Pb(BF4)2 and HBF4] by flame atomic absorption spectroscopy is described. This method is to be used as a routine analytical method in an industrial
quality control laboratory. To this end the "performance characteristics" of an instrumental analytical method such as matrix
effects, sensitivity, linearity, detection and quantitation limits, precision and accuracy were evaluated for every system
under study. The results of these investigations showed that non-spectral interferences (due to the presence of large concentrations
of major metals such as Cu, Sn and Pb) were observed. Nevertheless it was possible to define a matrix concentration interval
where matrix effects were not statistically significant, and therefore a direct calibration approach could be used as the
calibration tool whenever the major metal concentration was not higher than 40×10–3 kg l–1. A guide to the developement of an analytical method for trace metal determination is provided. General tools for quality
control have been used in order to show how an analytical method can be tested daily and evaluated in a convenient manner.
Received: 29 January 1997 Accepted: 11 March 1997 相似文献